Postmodification Approach to Charge-Tagged 1,2,4-Triazole-Derived NHC Palladium(II) Complexes and Their Applications

Van Ha Nguyen; Mansur B. Ibrahim; Waseem W. Mansour; Bassam M. El Ali; Han Vinh Huynh

doi:10.1021/acs.organomet.7b00329

Postmodification Approach to Charge-Tagged 1,2,4-Triazole-Derived NHC Palladium(II) Complexes and Their Applications

Van Ha Nguyen
, Mansur B. Ibrahim
, Waseem W. Mansour
, Bassam M. El Ali^*
, Han Vinh Huynh

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

34 Scopus citations

Abstract

Charge-tagged bis(1,2,4-triazolin-5-ylidene)palladium(II) complexes have been successfully synthesized via a postmodification strategy. Reacting PdBr₂ with bromo-functionalized 1,2,4-triazolium salts A·HBr and B·HBr in the presence of silver oxide afforded the bis(carbene)palladium(II) complexes trans-[PdBr₂(A)₂] (1a) and trans-[PdBr₂(B)₂] (1b), which contain tethered bromoalkyl chains. Subsequent postcoordinative nucleophilic substitution converted the bromo into ammonium groups, producing the water-soluble complexes trans-[PdBr₂(C)₂]Br₂ (2a) and trans-[PdBr₂(D)₂]Br₂ (2b), while attempts to prepare ammonium-functionalized triazolium salts for direct metalation were futile. All four complexes were fully characterized by means of multinuclear NMR spectroscopy, ESI mass spectrometry, elemental analysis, and X-ray diffraction analysis. The presence of trans-anti and trans-syn rotameric complexes in solution was elucidated by ¹H and ¹³C NMR spectroscopy and theoretical calculations. Additionally, the two charge-tagged complexes, 2a,b, were found to be highly active precatalysts for the Suzuki-Miyaura and Mizoroki-Heck reactions in ⁱPrOH/H₂O and molten TBAB as an ionic liquid.

Original language	English
Pages (from-to)	2345-2353
Number of pages	9
Journal	Organometallics
Volume	36
Issue number	12
DOIs	https://doi.org/10.1021/acs.organomet.7b00329
State	Published - 26 Jun 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

Access to Document

10.1021/acs.organomet.7b00329

Cite this

@article{455f9370584d4de098c9944d825d3f0d,

title = "Postmodification Approach to Charge-Tagged 1,2,4-Triazole-Derived NHC Palladium(II) Complexes and Their Applications",

abstract = "Charge-tagged bis(1,2,4-triazolin-5-ylidene)palladium(II) complexes have been successfully synthesized via a postmodification strategy. Reacting PdBr2 with bromo-functionalized 1,2,4-triazolium salts A·HBr and B·HBr in the presence of silver oxide afforded the bis(carbene)palladium(II) complexes trans-[PdBr2(A)2] (1a) and trans-[PdBr2(B)2] (1b), which contain tethered bromoalkyl chains. Subsequent postcoordinative nucleophilic substitution converted the bromo into ammonium groups, producing the water-soluble complexes trans-[PdBr2(C)2]Br2 (2a) and trans-[PdBr2(D)2]Br2 (2b), while attempts to prepare ammonium-functionalized triazolium salts for direct metalation were futile. All four complexes were fully characterized by means of multinuclear NMR spectroscopy, ESI mass spectrometry, elemental analysis, and X-ray diffraction analysis. The presence of trans-anti and trans-syn rotameric complexes in solution was elucidated by 1H and 13C NMR spectroscopy and theoretical calculations. Additionally, the two charge-tagged complexes, 2a,b, were found to be highly active precatalysts for the Suzuki-Miyaura and Mizoroki-Heck reactions in iPrOH/H2O and molten TBAB as an ionic liquid.",

author = "Nguyen, \{Van Ha\} and Ibrahim, \{Mansur B.\} and Mansour, \{Waseem W.\} and \{El Ali\}, \{Bassam M.\} and Huynh, \{Han Vinh\}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = jun,

day = "26",

doi = "10.1021/acs.organomet.7b00329",

language = "English",

volume = "36",

pages = "2345--2353",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Postmodification Approach to Charge-Tagged 1,2,4-Triazole-Derived NHC Palladium(II) Complexes and Their Applications

AU - Nguyen, Van Ha

AU - Ibrahim, Mansur B.

AU - Mansour, Waseem W.

AU - El Ali, Bassam M.

AU - Huynh, Han Vinh

PY - 2017/6/26

Y1 - 2017/6/26

N2 - Charge-tagged bis(1,2,4-triazolin-5-ylidene)palladium(II) complexes have been successfully synthesized via a postmodification strategy. Reacting PdBr2 with bromo-functionalized 1,2,4-triazolium salts A·HBr and B·HBr in the presence of silver oxide afforded the bis(carbene)palladium(II) complexes trans-[PdBr2(A)2] (1a) and trans-[PdBr2(B)2] (1b), which contain tethered bromoalkyl chains. Subsequent postcoordinative nucleophilic substitution converted the bromo into ammonium groups, producing the water-soluble complexes trans-[PdBr2(C)2]Br2 (2a) and trans-[PdBr2(D)2]Br2 (2b), while attempts to prepare ammonium-functionalized triazolium salts for direct metalation were futile. All four complexes were fully characterized by means of multinuclear NMR spectroscopy, ESI mass spectrometry, elemental analysis, and X-ray diffraction analysis. The presence of trans-anti and trans-syn rotameric complexes in solution was elucidated by 1H and 13C NMR spectroscopy and theoretical calculations. Additionally, the two charge-tagged complexes, 2a,b, were found to be highly active precatalysts for the Suzuki-Miyaura and Mizoroki-Heck reactions in iPrOH/H2O and molten TBAB as an ionic liquid.

AB - Charge-tagged bis(1,2,4-triazolin-5-ylidene)palladium(II) complexes have been successfully synthesized via a postmodification strategy. Reacting PdBr2 with bromo-functionalized 1,2,4-triazolium salts A·HBr and B·HBr in the presence of silver oxide afforded the bis(carbene)palladium(II) complexes trans-[PdBr2(A)2] (1a) and trans-[PdBr2(B)2] (1b), which contain tethered bromoalkyl chains. Subsequent postcoordinative nucleophilic substitution converted the bromo into ammonium groups, producing the water-soluble complexes trans-[PdBr2(C)2]Br2 (2a) and trans-[PdBr2(D)2]Br2 (2b), while attempts to prepare ammonium-functionalized triazolium salts for direct metalation were futile. All four complexes were fully characterized by means of multinuclear NMR spectroscopy, ESI mass spectrometry, elemental analysis, and X-ray diffraction analysis. The presence of trans-anti and trans-syn rotameric complexes in solution was elucidated by 1H and 13C NMR spectroscopy and theoretical calculations. Additionally, the two charge-tagged complexes, 2a,b, were found to be highly active precatalysts for the Suzuki-Miyaura and Mizoroki-Heck reactions in iPrOH/H2O and molten TBAB as an ionic liquid.

UR - https://www.scopus.com/pages/publications/85021266735

U2 - 10.1021/acs.organomet.7b00329

DO - 10.1021/acs.organomet.7b00329

M3 - Article

AN - SCOPUS:85021266735

SN - 0276-7333

VL - 36

SP - 2345

EP - 2353

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Postmodification Approach to Charge-Tagged 1,2,4-Triazole-Derived NHC Palladium(II) Complexes and Their Applications

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Fingerprint

Cite this